WO1993018110A1 - Melange refrigerant non azeotrope de r23, r125 et r32 - Google Patents

Melange refrigerant non azeotrope de r23, r125 et r32 Download PDF

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Publication number
WO1993018110A1
WO1993018110A1 PCT/CA1993/000082 CA9300082W WO9318110A1 WO 1993018110 A1 WO1993018110 A1 WO 1993018110A1 CA 9300082 W CA9300082 W CA 9300082W WO 9318110 A1 WO9318110 A1 WO 9318110A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
refrigerant
balance
azeotropic
heat
Prior art date
Application number
PCT/CA1993/000082
Other languages
English (en)
Inventor
Samuel Sami
Original Assignee
University Of Moncton
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Moncton filed Critical University Of Moncton
Priority to EP93906409A priority Critical patent/EP0629229B1/fr
Priority to AU37426/93A priority patent/AU3742693A/en
Priority to DE69303603T priority patent/DE69303603D1/de
Publication of WO1993018110A1 publication Critical patent/WO1993018110A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/34—The mixture being non-azeotropic

Definitions

  • This invention relates to a non-azeotropic refrigerant mixture, suitable as a working fluid for heat pump applications as well as in other vapour compression machines.
  • the mixture is entirely compatible with R22 and R502 refrigerants currently used in heat pumps, and so does not require changes in the design of such heat pumps.
  • R22 is chlorodifluoromethane (CHCLF 2 )
  • R502 is a mixture of R22 and R115 which is chloropentafluoroethane (CHClF 2 CHF3).
  • other vapour compression equipment can use the mixture as a drop-in replacement for presently used refrigerants, depending on the mixture composition.
  • the mixture is environmentally acceptable.
  • the the ⁇ nodynamic performance of an energy conversion device may be improved by using a non-azeotropic mixture in a vapour cycle.
  • a non-azeotropic mixture has a temperature distribution parallel to that of the surrounding fluid with which heat transfer takes place during the evaporation and condensation processes which are part of the cycle.
  • NARM N-oxide-semiconductor
  • these have two components, but some having three (i.e. ternary mixtures) have been proposed, for example in:
  • the present invention provides a ternary non-azeotropic mixture which has similar advantages over R22 as does the mixture of PCT Serial No. PCT/CA92/00208 but in which no chlorinated compounds are used; instead the mixture contains only hydrofluorocarbons (HFC's), such as pentafluoroethane (R.125) and methylene fluoride (R32), also known as difluoromethane. Since the mixture of this invention contains no chlorine it is environmentally safe. R125 has a molecular weight of 120.02 and boils at -48.50°C; it is non-flammable.
  • HFC's hydrofluorocarbons
  • R.125 pentafluoroethane
  • R32 methylene fluoride
  • R32 has a molecular weight of 79.20 and boils at -51.61°C and is non-flammable at concentrations not higher than 65% in a mixture.
  • the third component, R23 has a molecular weight of 70.02 and boils at -82.06°C and is non-flammable.
  • the present invention provides a unique non-azeotropic refrigerant mixture containing R23, R125, and R32 refrigerants which has a remarkably good coefficient of performance without sacrificing either thermal capacity or environmentally desirable properties.
  • a refrigerant for use in a heat pump or other equipment designed for R22 or R502, without modification of the equipment comprises a ternary non-azeotropic mixture of known refrigerants, as follows:
  • R32 (CH 2 F 2 ; methylene fluoride or
  • composition of the mixture will vary with particular working conditions; however the mixtures will all be within this broad range to avoid degraded performance, high condenser operating pressures which are incompatible with existing equipment, and flammability of the mixture.
  • composition (c) 5% 70% 25%
  • Fig. 1 are graphs showing how coefficient of performance for refrigeration changes with temperature for pure refrigerant R22; R502 which is a mixture of R22 and R115 having a boiling point of -45.44°C and molecular weight 111.63; and mixtures in accordance with the invention;
  • Figs. 2 through 6 show graphs of performance characteristics vs temperature at the inlet to the liquid evaporator, for the different refrigerant compositions shown above;
  • Figs. 7 and 8 show how the coefficient of performance of a heat pump varies with volumetric cooling capacity for different refrigerants
  • Fig. 9 shows a graph of pressure against temperature for different refrigerants
  • Figs. 10 and 11 show graphs of the volumetric capacity for heating and cooling respectively, against temperature, both for Applicant's mixture and mixtures of other HFC's;
  • Fig. 12 shows a graph of pressure against temperature for the same mixtures as Figs. 10 and 11. 5. Detailed Description:
  • An azeotropic mixture of two substances or more cannot be separated into its components by distillation. Such a mixture evaporates and condenses as a single substance with properties that are different from those of either constituent. Whereas pure substances or azeotropic mixtures have a constant phase changing temperature (e.g. boiling point) at a given pressure, a non-azeotropic mixture condenses and boils over a temperature range by an isobaric heating process.
  • phase changing temperature e.g. boiling point
  • Refrigerant Mixtures are as follows:
  • CDS Carnhan-Starling-DeSantis
  • Fig. 9 shows that the proposed compositions behave as a homogenous refrigerant over the investigated range having pressure/temperature characteristics similar to R22 and R502. This is a significant characteristic, since handling and packaging expose the refrigerant to various temperatures.
  • the similarity to R22 and R502 means that standard equipment which uses R22 or R502 can utilize this mixture without modification.
  • the proposed non-azeotropic mixture is non-flammable.
  • ODP Depletion Potential
  • the three components R23, R32 and R125 also have very low Greenhouse Depletion Potential (GDP) of less than 0.1.
  • GDP Greenhouse Depletion Potential
  • mixtures of the said refrigerants as described herein has been found to result in very desirable mixtures in attaining low evaporating temperatures and a reasonable head pressure and can be used with conventional heat pumps or other machines designed for R22 and/or R502 without the requirement for any major modifications or change in equipment.
  • This heat pump comprises an air/refrigerant evaporator into which the mixture is introduced and from which it is discharged to a hermetic compressor for compressing the vapour mixture into an air finned condenser. After condensation, the mixture is discharged to an expansion valve; it is finally expanded through the expansion valve and recycled to the evaporator. Evaluations of performance have been made with the refrigerant mixtures using air temperatures at the evaporator from -30°C to 5°C at constant air temperature of 27°C at the inlet to the air condenser.
  • Figs. 7 and 8 Samples of further performance results, obtained at entering air temperature to the evaporator from -30°C to 5°C and air entering temperature to the condenser of 35°C are displayed in Figs. 7 and 8.
  • the coefficient of performance (COPR) shown in Figs. 1 through 8 is defined as the ratio of the heat powder delivered by the heat pump to the electric power consumed by the motor which drives the compressor.
  • Fig. 9 shows the proposed mixture of the present invention, containing R23/R125/R32; which in the high temperature range has properties higher than that of pure R22. However, these proposed concentrations can be employed in equipment designed for R22, since their head pressure is below the equipment design pressure.
  • Figs. 10 through 12 show a comparison between a mixture of
  • MIXING COEFFICIENTS 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
  • MIXING COEFFICIENT S 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
  • MIXING COEFFICIENTS 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On utilise un mélange réfrigérant non azéotrope dans les pompes à chaleur pour en améliorer le rendement, calculé en coefficient de performance et en capacité de compression, par rapport aux réfrigérants ou mélanges de réfrigérants existants. Ce réfrigérant est un mélange ternaire de 1 à 10 % de R23 (trifluorométhane), 1 à 70 % de R125 (pentafluroéthane), l'appoint étant constitué de R32 (fluorure de méthylène; difluorométhane). On peut utiliser ce mélange dans les pompes à chaleur et dans d'autres machines conçues pour le R22 et/ou le R502 sans modification, et il se révèle acceptable du point de vue écologique.
PCT/CA1993/000082 1992-03-03 1993-03-03 Melange refrigerant non azeotrope de r23, r125 et r32 WO1993018110A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP93906409A EP0629229B1 (fr) 1992-03-03 1993-03-03 Melange refrigerant non azeotrope de r23, r125 et r32
AU37426/93A AU3742693A (en) 1992-03-03 1993-03-03 Non-azeotropic refrigerant mixture of r23, r125 and r32
DE69303603T DE69303603D1 (de) 1992-03-03 1993-03-03 Nichtazeotrope kaeltemittelmischung aus r23, r125 und r32

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84507692A 1992-03-03 1992-03-03
US07/845,076 1992-03-03

Publications (1)

Publication Number Publication Date
WO1993018110A1 true WO1993018110A1 (fr) 1993-09-16

Family

ID=25294340

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1993/000082 WO1993018110A1 (fr) 1992-03-03 1993-03-03 Melange refrigerant non azeotrope de r23, r125 et r32

Country Status (3)

Country Link
EP (1) EP0629229B1 (fr)
DE (1) DE69303603D1 (fr)
WO (1) WO1993018110A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
US5736063A (en) * 1991-03-18 1998-04-07 Alliedsignal Inc. Non-azeotropic refrigerant compositions containing carbon dioxide
FR2756294A1 (fr) * 1996-11-27 1998-05-29 Atochem Elf Sa Utilisation de melanges a base de difluoromethane et de pentafluoroethane comme fluides frigorigenes en refrigeration tres basse temperature

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430171A1 (fr) * 1989-11-30 1991-06-05 Matsushita Electric Industrial Co., Ltd. Fluide de travail
US5066410A (en) * 1989-05-02 1991-11-19 Daikin Industries, Ltd. Refrigerating machine composition comprising a fluorine-containing polyether oil
WO1992015658A1 (fr) * 1991-03-05 1992-09-17 Imperial Chemical Industries Plc Lubrifiants pour installations de transfert de chaleur
WO1992016597A1 (fr) * 1991-03-18 1992-10-01 Allied-Signal Inc. Compositions refrigerantes non azeotropes comprenant du difluoromethane, du 1,1,1-trifluoroethane ou du propane
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5066410A (en) * 1989-05-02 1991-11-19 Daikin Industries, Ltd. Refrigerating machine composition comprising a fluorine-containing polyether oil
EP0430171A1 (fr) * 1989-11-30 1991-06-05 Matsushita Electric Industrial Co., Ltd. Fluide de travail
WO1992015658A1 (fr) * 1991-03-05 1992-09-17 Imperial Chemical Industries Plc Lubrifiants pour installations de transfert de chaleur
WO1992016597A1 (fr) * 1991-03-18 1992-10-01 Allied-Signal Inc. Compositions refrigerantes non azeotropes comprenant du difluoromethane, du 1,1,1-trifluoroethane ou du propane
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5736063A (en) * 1991-03-18 1998-04-07 Alliedsignal Inc. Non-azeotropic refrigerant compositions containing carbon dioxide
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
FR2756294A1 (fr) * 1996-11-27 1998-05-29 Atochem Elf Sa Utilisation de melanges a base de difluoromethane et de pentafluoroethane comme fluides frigorigenes en refrigeration tres basse temperature
EP0845519A1 (fr) * 1996-11-27 1998-06-03 Elf Atochem S.A. Utilisation de mélanges à base de difluorométhane et de pentafluoroéthane comme fluides frigorigènes en réfrigération tres basse température
US6093340A (en) * 1996-11-27 2000-07-25 Elf Atochem S.A. Use of mixtures based on difluoromethane and on pentafluorethane as cryogenic fluids in very low temperature refrigeration
AU736218B2 (en) * 1996-11-27 2001-07-26 Elf Atochem S.A. Use of mixtures based on difluoromethane and on pentafluoroethane as cryogenic fluids in very low temperature refrigeration

Also Published As

Publication number Publication date
EP0629229B1 (fr) 1996-07-10
DE69303603D1 (de) 1996-08-14
EP0629229A1 (fr) 1994-12-21

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